CN102405259A - Composition for polyimide resin and polyimide resin comprising same - Google Patents

Composition for polyimide resin and polyimide resin comprising same Download PDF

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Publication number
CN102405259A
CN102405259A CN201080002788XA CN201080002788A CN102405259A CN 102405259 A CN102405259 A CN 102405259A CN 201080002788X A CN201080002788X A CN 201080002788XA CN 201080002788 A CN201080002788 A CN 201080002788A CN 102405259 A CN102405259 A CN 102405259A
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China
Prior art keywords
polyimide resin
tectum
metal
composition
polyimide
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Granted
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CN201080002788XA
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Chinese (zh)
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CN102405259B (en
Inventor
松山浩幸
田井诚
岩野畅行
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Arisawa Mfg Co Ltd
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Arisawa Mfg Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C08K5/3447—Five-membered rings condensed with carbocyclic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/202—Conductive
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
    • B32B2307/204—Di-electric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • B32B2307/3065—Flame resistant or retardant, fire resistant or retardant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/40—Properties of the layers or laminate having particular optical properties
    • B32B2307/41—Opaque
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/03—Use of materials for the substrate
    • H05K1/0313—Organic insulating material
    • H05K1/032—Organic insulating material consisting of one material
    • H05K1/0346—Organic insulating material consisting of one material containing N
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0154—Polyimide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/287—Adhesive compositions including epoxy group or epoxy polymer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2887—Adhesive compositions including addition polymer from unsaturated monomer including nitrogen containing polymer [e.g., polyacrylonitrile, polymethacrylonitrile, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
    • Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
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    • Y10T428/2852—Adhesive compositions
    • Y10T428/2896—Adhesive compositions including nitrogen containing condensation polymer [e.g., polyurethane, polyisocyanate, etc.]
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    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31721—Of polyimide

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Disclosed is a composition for a polyimide resin comprising a polyamic acid and a perylene black pigment having an isoindole skeleton, wherein the content of the perylene black pigment is 1 to 10% by mass with respect to 100% by mass of the solid content of the polyamic acid.

Description

Polyimide resin is with composition and by its polyimide resin that forms
Technical field
The present invention relates to polyimide resin that a kind of new type polyimide resin constitutes with composition with composition and by this polyimide resin and metal-coated laminated board, tectum (cover lay) and flexible printing wiring board.
Background technology
Available technology adopting is flexible printing wiring boards (FPC) such as the tectum that forms of appropriate combination such as metal foil layer such as the bond layer of major ingredient and the Copper Foil with electroconductibility, silver foil, aluminium foil or metal-coated laminated board by resin layers such as polyimide film with electrical insulating property or polyamide membrane, with Resins, epoxy or polyimide resin.
Known metal-coated laminated board has three layers of flexible metal veneer sheet that are made up of adhesive linkages such as metal level, polyimide layer and Resins, epoxy and the double-deck flexible metal veneer sheet that is made up of metal level that comprises tinsel and polyimide layer.
Recently, the flexible metal veneer sheet is used for electronics and optical device more and more, and the opacifying property to the flexible metal veneer sheet requires also to improve gradually thus.For example, the method that illuminates portable display has the area source mode and light source illuminates whole indicating meter through light guiding plate etc. mode is set in the end.In order to illuminate indicating meter effectively, this dual mode has all carried out careful calculating and design.But area source and this dual mode of end light source all exist from indicating meter flexible printing wiring board light leak, the result on every side that pack into and cause the problem to outside light leak from the housing junction surface.As the technology that addresses this problem, known have the pigment of the light through being mixed for absorbing all wavelengths to make polyimide layer become the technology of black.
For example, the opacifying property mulch film that makes one of electrically insulating film and Thermocurable caking agent or both contain the black pigment with specific median size is disclosed in the patent documentation 1.
And, a kind of flexible printing wiring substrate is disclosed in the patent documentation 2, wherein one of insulated substrate and tectum or both are the para-orientation (paraorientation that contains dyestuff more than 1% by weight or pigment) type aromatic polyamide film.
The prior art document
Patent documentation
Patent documentation 1: japanese kokai publication hei 9-135067 communique
Patent documentation 2: japanese kokai publication hei 6-350120 communique
Summary of the invention
Invent problem to be solved
But, described in patent documentation 1, use carbon black during as black pigment with electroconductibility, have that insulativity reduces, the shortcoming of electrical specification difference.
And when using organic dye described in the patent documentation 2 or pigment dyestuff; In field of electronic materials, under high-temperature and high-pressure conditions, carry out the materials processing operation or when making polyimide film, carry out in the process of high temperature process operation, exist dyestuff or pigment to decompose or distillation causes obtaining the problem of stable black.
In view of the above problems, problem to be solved by this invention is to provide a kind of polyimide resin composition that can obtain to have concurrently the polyimide resin of excellent opacifying property and electrical specification.
The means of technical solution problem
In order to solve above-mentioned problem, the inventor finds that containing polyamic acid with specified proportion can address the above problem with composition with the polyimide resin with isoindole skeleton De perylene mineral black, and has accomplished the present invention through deep research.
That is, technical scheme of the present invention is following:
[1 polyimide resin composition; Wherein, Said polyimide resin contains polyamic acid with composition and has isoindole skeleton De perylene mineral black; Be in mass 100% with respect to the solids component weight of above-mentioned polyamic acid, the content of Shang Shu perylene mineral black is in mass 1%～10%.
[2 is according to above-mentioned [1] described polyimide resin composition, and wherein, Shang Shu perylene mineral black has the structure shown in the following general formula (1),
[chemical formula 1]
In the formula (1), X representes to have the organic residue of divalence of the isoindole skeleton shown in the following general formula (2),
[chemical formula 2]
In the formula (2), R1, R2, R3 and R4 can be identical or different, and expression hydrogen atom or carbonatoms are 1 to 6 alkyl.
One kind of [3 is through solidifying the polyimide resin that gets with above-mentioned [1] or [2] described polyimide resin with composition.
One kind of [4 is through being pressed in the metal-coated laminated board that gets on the tinsel with above-mentioned [3] described polyimide resin layer.
[5 is according to above-mentioned [4] described metal-coated laminated board, and wherein, above-mentioned metal-coated laminated board is a double-deck flexible metal veneer sheet.
[6 tectum that comprises the polyimide film that forms by above-mentioned [3] described polyimide resin.
[7 is according to above-mentioned [6] described tectum, and wherein, above-mentioned tectum also comprises bond layer.
[8 is according to above-mentioned [7] described tectum, and wherein, above-mentioned bond layer contains more than one the resin that is selected from the group of being made up of Resins, epoxy, phenoxy resin, vinylformic acid (class) resin and urethane resin.
One kind of [9 is through being arranged on the flexible printing wiring board that gets on the tinsel that is formed with circuit with each described tectum in above-mentioned [6] to [8].
The invention effect
According to the present invention, can provide to have the excellent opacifying property and the polyimide resin of electrical specification concurrently.
Embodiment
Below, the mode (calling " this embodiment " in the following text) that is used for embodiment of the present invention is described in detail.In addition, the invention is not restricted to following embodiment, in the scope that does not break away from its aim, can carry out various distortion.
The polyimide resin of this embodiment contains polyamic acid with composition and has isoindole skeleton De perylene mineral black; If wherein the solids component weight of above-mentioned polyamic acid is in mass 100%, the content of then Shanging Shu perylene mineral black is adjusted in mass 1%～10%.
[polyamic acid]
Polyamic acid in this embodiment is not special to be limited, and can tetracarboxylic dianhydride and diamine compound be carried out polycondensation through known (solution polymerization) method and obtain.
Tetracarboxylic dianhydride and diamine compound can adopt any in fatty compounds and the aromatics, but from stable on heating viewpoint, preferably adopt aromatics.
Aromatic tetracarboxylic acid's dianhydride is not special to be limited, and for example can enumerate pyromellitic acid anhydride, 3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenonetetracarboxylic dianhydride, the two Tetra hydro Phthalic anhydrides and 3 of 4 '-oxygen, 3 ', 4,4 '-diphenylsulfone acid dianhydride etc.Wherein, from according to price be prone to the viewpoint of the property obtained, preferred 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride and pyromellitic acid anhydride.
Aromatic diamine compound is not special to be limited; For example can enumerate the p-phenylenediamine; The m-phenylenediamine; 2; 4-diaminotoluene '-benzidine '-diamino-2 '-two (trifluoromethyl) biphenyl '-diaminodiphenylsulfone(DDS) '-diaminodiphenylsulfone(DDS) '-diaminodiphenyl sulfide '-diaminodiphenylmethane '-diaminodiphenyl oxide, 4 '-diaminodiphenyl oxide, 3 ' diaminodiphenyl oxide; 1; Two (4-amino-benzene oxygen) benzene of 4-; 1; Two (4-amino-benzene oxygen) benzene of 3-, two (3-amino-benzene oxygen) benzene of 3-, 4 '-two (4-amino-benzene oxygen) biphenyl; Two [4-(4-amino-benzene oxygens) phenyl] sulfone; Two [4-(3-amino-benzene oxygens) phenyl] sulfone; 2; The two [4-(4-amino-benzene oxygens of 2-) phenyl] propane and 2, the two [4-(4-amino-benzene oxygens of 2-) phenyl] HFC-236fa etc.Wherein, from price and the viewpoint that is prone to the property obtained, preferred p-phenylenediamine and 4,4 '-diaminodiphenyl oxide and 1, two (4-amino-benzene oxygen) benzene of 3-.
In addition, above-mentioned tetracarboxylic dianhydride and diamine compound can use separately or two or more and usefulness.
In this embodiment; After for example in solvent, adding diamine compound; Under the temperature of room temperature to 30 ℃, make its dissolving; In gained solution, slowly add the tetracarboxylic dianhydride then; And at room temperature stir more than half an hour, can obtain polyamic acid thus as the precursor resin of polyimide resin.At this moment, can not make diamine compound dissolving and under dispersion state, add the tetracarboxylic dianhydride, also can in solvent, add after the tetracarboxylic dianhydride, dissolve or dispersion state under add diamine compound.Then, through at room temperature stirring more than half an hour, can obtain polyamic acid.And, the scope of whipping temp-10 ℃ to the scope of solvent boiling point and churning time be half an hour when above, also can obtain the polyamic acid of this embodiment.
[perylene mineral black]
This embodiment have that isoindole skeleton De perylene mineral black (be designated hereinafter simply as “ perylene mineral black ") is not special to be limited, but preferably have the structure shown in the formula (1) from the equilibrated viewpoint ， perylene mineral black of the transparency and electrical specification.
[chemical formula 3]
Figure BDA0000053345540000061
In the formula (1), the organic residue of divalence of X representes the to have formula isoindole skeleton shown in (2).
[chemical formula 4]
Figure BDA0000053345540000062
In the formula (2), R1, R2, R3 and R4 can be identical or different, and expression hydrogen atom or carbonatoms are 1 to 6 alkyl.
Here, be 1 to 6 alkyl as carbonatoms, for example can enumerate commutable alkyl, commutable cycloalkyl and commutable phenyl etc.
" alkyl " expression carbonatoms in the commutable alkyl is 1 to 6, preferred 1 to 3 straight chain shape or branched-chain alkyl; For example methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group and hexyl etc.; Preferable methyl and ethyl, more preferably methyl.
" cycloalkyl " expression carbonatoms in the commutable cycloalkyl is 3 to 6 cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl etc. is for example arranged, preferred cyclopentyl and cyclohexyl.
Abovementioned alkyl, cycloalkyl and phenyl can be replaced by one or more substituting group in the instead position.It is 1 to 6 alkyl (like methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, sec-butyl, the tertiary butyl, amyl group, hexyl), aryl (like phenyl, naphthyl), aralkyl (like phenmethyl, styroyl) and alkoxyl group (like methoxyl group, oxyethyl group) etc. that substituting group for example can be enumerated halogen atom (like fluorine atom, chlorine atom, bromine atoms), carbonatoms.
The polyimide resin of this embodiment is with in the composition; If the solids component weight of above-mentioned polyamic acid is in mass 100%; The content that then has an isoindole skeleton De perylene mineral black is in mass 1%～10%; Preferably in mass 2%～8%, further preferably in mass 3%～6%.If the content of Shang Shu perylene mineral black is lower than in mass 1%, light transmission improves, and therefore is difficult to give sufficient opacifying property to polyimide resin, and surpasses in mass 10% like the content of Guo perylene mineral black, and then the electrical specification of polyimide resin reduces.
Polyimide resin in this embodiment with composition except containing polyamic acid with the perylene mineral black, can also contain solvent.Solvent for example can be enumerated aprotic polar solvents such as N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-and gamma-butyrolactone.Solvent is preferably the solvent that is selected from the group of being made up of N,N-dimethylacetamide and N-N-methyl-2-2-pyrrolidone N-.
The content of solvent is preferably polyimide resin in mass with 80%～90% of total composition.Be made as in mass 80%～90% through content, can obtain the excellent lacquer viscosity of coating solvent.In this embodiment, " total amount " is meant the quality of polyimide resin with the solvent components in the composition." solids component " is meant solid itself, and " solvent components " is meant the solids component that is dissolved in the state behind the solvent.The content of solvent can be through the ((solvent quality)/(polyimide resin is with the quality) of total composition) * 100 are obtained.
The polyimide resin of this embodiment for example can obtain through with specified proportion above-mentioned polyamic acid Yu perylene mineral black being mixed in solvent with composition.And the polyimide resin of this embodiment uses can also add in the composition with acid anhydrides such as tertiary amines such as pyridine, Glacial acetic acids and is flow agent and fillers such as the imidization promotor of representative, tensio-active agent.And, in order to obtain better flame retardant resistance, can also mix fire retardant in composition at the polyimide resin of this embodiment.Fire retardant for example has organo phosphorous compoundss such as mineral fillers such as white lake, silicon-dioxide, barium sulfate or phosphoric acid ester.These fire retardants can use separately or and use.
[metal-coated laminated board]
Metal-coated laminated board in this embodiment is to obtain through being pressed on the tinsel by the polyimide resin layer that above-mentioned polyimide resin obtains with composition curing.
Metal-coated laminated board can be any in three layers of flexible metal veneer sheet being made up of tinsel, polyimide resin layer and adhesive linkage and the double-deck flexible metal veneer sheet that is made up of tinsel and polyimide resin layer; But from thermotolerance, dimensional stability and light-weighted viewpoint, preferred double-deck flexible metal veneer sheet.
Tinsel for example has Copper Foil, SUS(Steel Use Stainless) paper tinsel and aluminium foil etc., but from the viewpoint of electroconductibility and circuit fabrication property, preferred Copper Foil.And, when using tinsel, can carry out inorganic surfaces through zinc-plated, chromium plating etc. and handle and utilize silane coupling agent etc. to carry out organic surface treatment.
The double-deck flexible metal veneer sheet of this embodiment is for example through being included in coating polyimide resin on the tinsel with the operation of composition, carry out the exsiccant operation with composition and be warming up to 330 ℃～400 ℃ methods with the operation that obtains polyimide resin layer processing to being coated in above-mentioned polyimide resin on the above-mentioned tinsel.
In above-mentioned coating operation, the thickness that is formed on the coat on the tinsel is different and different according to purposes, can suitably be set between 2 μ m～150 μ m.For coating method, can suitably adopt comma coating machine (comma coater according to coating thickness), slit coater (die coater) and engraved roll coater (gravure coater) etc.
Polyimide resin to being coated on the above-mentioned tinsel carries out the exsiccant operation preferably through carrying out in dry 1 minute to 30 minutes down at 80 ℃～150 ℃ with composition.Through coating and drying process after the residual solvent amount preferably with respect to 100% polyamic acid in mass in mass below 50%.
Metal-coated laminated board also can be processed through following separation formation method.
At first; At the PET(polyethylene terephthalate) film, PP(polypropylene) film, PE(Vilaterm) after the coating polyimide resin forms coat with composition on the mold release film such as film; (temperature is 80 ℃～160 ℃ at certain curing drying conditions; Time is 1 minute to 30 minutes) solidify down and be dried to semi-cured state (below be also referred to as " B stage "), thus obtain polyimide resin layer.Handle through the surface of mold release film being carried out the demoulding, can improve the separability of itself and polyimide resin layer.
Then, the uneven surface of the resin face of polyimide resin layer and tinsel is bonding and process metal-coated laminated board.Adhesive bonding method can adopt the laminating of pressing and use hot-rolling etc.For bond condition, preferably under the pressure of 200 ℃～350 ℃ temperature and 0.5MPa～5MPa scope, carry out bonding.
Above the single face metal-coated laminated board is illustrated, but also can uses the two-sided metal-coated laminated board that on two faces of polyimide resin layer, all is provided with tinsel.Two-sided metal-coated laminated board can be through being provided with tinsel on two faces of the made resin sheet of above-mentioned separation formation method, utilize above-mentioned adhesive bonding method to carry out hot pressing then and fetch and process.
The metal-coated laminated board of this embodiment is owing to contain special quantitative perylene mineral black in polyimide resin layer, therefore have also excellent characteristics very of opacifying property excellence and electrical specifications such as specific inductivity and dielectric tangent.
And; Therefore the metal-coated laminated board of this embodiment has good dimensional stability owing to contain the polyimide resin that is formed by the polyamic acid condensation, and in the state that adds man-hour and the finished product; Therefore peeling off etc. of rare metal line improved product life.
And, because polyimide resin layer has thermotolerance,, also can tackle even therefore processing temperature is a high temperature, need not cooling and just can process.Therefore, shortened process period.And the processibility of formation and semiconductor element mounting etc. and the metal-coated laminated board that yield rate improves can obtain connecting up.
Metal level through with the metal-coated laminated board of this embodiment is etched into the regulation shape, and the etching face that obtains is covered through the tectum that is used to cover metal-foil circuits, can obtain the circuit that covers through tectum.As long as tectum can cover metal-foil circuits, there is not qualification especially, for example have through on films such as polyimide, applying tectum, liquid resist layer and the dry film resist layer etc. that caking agent obtains.
From the viewpoint of dimensional stability, the coefficient of linear thermal expansion CTE(10 of the polyimide resin layer that contains in the metal-coated laminated board < >-6 <> / K) preferably 25 * 10 < >-6 <> Below the /K, more preferably 23 * 10 < >-6 <> Below the /K.
The transmittance of the polyimide resin layer that contains in the metal-coated laminated board (%) is preferably below 1%.When the transmittance of polyimide resin layer 1% when following; The opacifying property that contains metal-coated laminated board or the flexible printing wiring board etc. of this polyimide resin layer improves; Therefore the light source light leak tails off, thereby improves in the visuality of the display parts such as state knob down of the finished product.
For the form and aspect of the polyimide resin layer that contains in the metal-coated laminated board, preferred a < > * <> Value is-5～5, b < > * <> Value is-10～10, L < > * <> Value is below 5, further preferred-4～4.When the form and aspect of polyimide resin layer are in above-mentioned scope; The opacifying property that contains metal-coated laminated board or the flexible printing wiring board etc. of this polyimide resin layer improves; Therefore the light source light leak tails off, thereby improves in the visuality of the display parts such as state knob down of the finished product.
Here, a < > * <> Value and b < > * <> Value is " the color index " of expression form and aspect and chroma, L < > * <> Value is " brightness index ".
From stable on heating viewpoint, in the metal-coated laminated board glass transition temp Tg(of contained polyimide resin layer ℃) be preferably 300 ℃～400 ℃, further be preferably more than 310 ℃.
The breakdown voltage resistant (V/mm of contained polyimide resin layer in the metal-coated laminated board) preferably more than 150V/mm, more than the further preferred 175V/mm.When polyimide resin layer breakdown voltage resistant was in above-mentioned scope, the electrical specification that contains metal-coated laminated board or the flexible printing wiring board etc. of this polyimide resin layer improved.
The specific inductivity of contained polyimide resin layer is preferably below 4.0, further preferably below 3.5 in the metal-coated laminated board.And its dielectric tangent is preferably below 0.02, further preferably below 0.01.When the specific inductivity of polyimide resin layer and dielectric tangent were in above-mentioned scope, the electrical specification that contains metal-coated laminated board or the flexible printing wiring board etc. of this polyimide resin layer improved.
Here, above-mentioned CTE, transmittance, form and aspect, Tg, breakdown voltage resistant, specific inductivity and dielectric tangent can be measured through the described method of following examples.
[tectum]
Tectum in this embodiment comprises the polyimide film that is formed by above-mentioned polyimide resin.
Tectal structure is not special to be limited; Usually; Except comprising the resin layer that constitutes by polyimide film, also comprise the tectum of bond layer owing to contain the resin layer that constitutes by above-mentioned polyimide film, therefore have opacifying property and electrical specification excellent characteristics.And, also have excellent flame, welding thermotolerance and the distinctive circuit imbedibility of tectum, and can keep high adhesion.And the tectum that is made up of polyimide film and mold release film can also be realized lightening except These characteristics.And the tectum of this embodiment can adopt the manufacturing process of existing flexible printing wiring board and need not make improvements, and therefore aspect equipment, has also reduced production cost.
The bond layer that is contained in the tectum is not special to be limited, and for example can contain more than one the resin that is selected from Resins, epoxy, phenoxy resin, acrylic resin and the urethane resin.And, according to the kind of above-mentioned resin, can also in bond layer, add additives such as solidifying agent.
If tectum is made up of for example polyimide film and mold release film, then tectal method of manufacture can be carried out through using above-mentioned separation formation method on mold release film, to form polyimide resin layer.In separating the formation method, polyimide resin layer need not completely solidified, but solidifies the semi-cured state (B stage that is dried to down at certain curing drying conditions (temperature is 80 ℃～160 ℃, and the time is 1 minute to 30 minutes)) obtain polyimide resin layer.And mold release film can be arranged on two faces of polyimide resin layer, uses through suitably it being peeled off during use.
And, when tectum also contains bond layer, under certain curing drying conditions (temperature is 300 ℃～400 ℃, and the time is 1 minute to 30 minutes), the made polyimide resin layer of above-mentioned separation formation method is almost completely solidified.In order to form adhesive linkage, under certain curing drying conditions (temperature is 80 ℃～160 ℃, and the time is 1 minute to 30 minutes), bond layer is solidified the semi-cured state (B stage that is dried on above-mentioned polyimide resin layer then) obtain bond layer.In addition, condition of cure can suitably be adjusted according to the resin of host and the amount of solidifying agent etc.And mold release film can be arranged on two faces, uses through suitably it being peeled off during use.
[flexible printing wiring board]
Flexible printing wiring board in this embodiment is processed through above-mentioned tectum is arranged on the tinsel that forms circuit.The thickness of the flexible printing wiring board in this embodiment can be set arbitrarily according to its purposes.
In the flexible printing wiring board, if tectum is made up of polyimide film and mold release film, then this tectum also has the function of the interlayer caking agent (adhesive sheet) that is used for multilayer printed-wiring board.Specifically, on flexible printing wiring board, through tectum being laminated on the circuit formation face that is exposed on the tinsel, and at these other flexible printing wiring boards of tectum laminated, and under prescribed condition heating and pressurizing, can process multilayer printed-wiring board.Therefore, need not to be used for and on circuit formation face, to be provided with the adhesive sheet that tectal flexible printing wiring board engages, thereby can realize the lightening of multilayer printed-wiring board, and can obtain more highdensity multilayer printed-wiring board.In addition,, need make tectum have enough thickness, not contact each other so that foregoing circuit forms face in that the circuit of flexible printing wiring board to be formed face mutual when laminated together.
The flexible printing wiring board of this embodiment is preferably used as the so-called Chip Packaging formula (chip on that for example is used to install the IC chip) flexible printing wiring board.
Embodiment
According to embodiment and comparative example the present invention is further specified below, the present invention is not limited only to these embodiment.
The acid anhydrides composition that uses in embodiment and the comparative example, diamines composition, solvent Yi are Ji the perylene mineral black is following:
(acid anhydrides composition)
BPDA:3,4,3 ', 4 '-biphenyl tetracarboxylic dianhydride (Ube Industries Ltd.'s manufactured)
MDA: anhydrous pyromellitic acid anhydride (Japanese Daicel chemical industrial company make)
(diamines composition)
P-PDA:p-phenylenediamine (Japanese the Northeast chemical company make)
4,4 '-DAPE:4,4 '-diaminodiphenyl oxide (Japanese Wakayama refine manufactured)
(solvent)
NMP:N-N-methyl-2-2-pyrrolidone N-(Japanese the Northeast chemical company make)
(having isoindole skeleton De perylene mineral black)
FK4280:LUMOGEN Black FK4280(Germany BASF (BASF) manufactured)
FK4280 is formula (3) and (4) represented mixture of isomers.
[chemical formula 5]
Qi Ta perylene mineral black of ()
L-0086:Paliogen Black L-0086(BASF Aktiengesellschaft makes)
S-0084:Paliogen Black S-0084(BASF Aktiengesellschaft makes)
Here, L-0086 is for to have mehtoxybenzyl De perylene mineral black at the molecular end Y of formula (5), and S-0084 is for to have phenylethyl De perylene mineral black at the molecular end Y of formula (5).
[chemical formula 6]
Figure BDA0000053345540000151
Evaluation method and measuring method in embodiment and the comparative example are following.In addition, each is measured and all adopts polyimide film, and this polyimide film is removed through the Copper Foil on the double-deck flexible copper-clad veneer sheet that will obtain in embodiment and the comparative example and obtained.
(1)CTE measures
The thermo-mechanical analysis device TMA-60 that adopts Shimadzu Corp to make, sampling originally is of a size of wide 5mm, long 15mm, and heavy burden 5g heats with the heat-up rate of 10 ℃ of /min, and 100 ℃ to 200 ℃ dimensional change is obtained CTE when heating.
(2) transmittance and a < > * <> Value, b < > * <> Value and L < > * <> Value
The spectrophotometer U-4100 that adopts FDAC to make manufacturing obtains the transmissivity of 500nm wavelength.
The spectrophotometer U-4100 that adopts FDAC to make manufacturing measures the transmissivity of 80nm～80nm wavelength, thereby obtains a < > * <> Value, b < > * <> Value and L < > * <> Value.
(3) Tg measures
Adopting U.S. rheology science (Rheometric Scientific) the Measurement of Dynamic Viscoelasticity device RSAII of the manufactured dynamic viscoelastic when heating up with 10 ℃ of /min measures, and obtains Tg according to the maximum value of tan δ.
(4) breakdown voltage resistant
The compression tester HVT-200-5 that uses Japanese mountain water chestnut electric corporation to make, film thickness direction makes voltage rise with 0.5kV/sec relatively, will arrive voltage till conducting electricity as voltage breakdown.
(5) specific inductivity and dielectric tangent
Adopt Agilent science and technology (Agilent Technologies) the PNA-L NetworkAnalyzer N-5230A of manufactured is through division back dielectric resonator method (split post dielectric resonator, SPDR method) obtain specific inductivity and dielectric tangent under the 5GHz frequency.
[embodiment 1]
In the flask of 500L, add the NMP of 255g as polymer solvent.Then, add 9.4g(0.087mo1)p-PDA and 4.3g(0.022mo1)4 as the diamines composition, 4 '-DAPE stirs under 30 ℃ then, makes diamines composition p-PDA and 4, and 4 '-DAPE is dissolved in NMP.
In gained solution, slowly add 25.6g(0.087mo1 simultaneously as the acid anhydrides composition) BPDA and 4.8g(0.022mo1) PMDA.
Then, at room temperature stirred 10 hours, thereby obtain polyamic acid resin solution.In the resulting polyamic acid resin solution of 100g, the solids component weight of polyamic acid is 15g.Here, the solids component weight of polyamic acid is calculated according to the adding quality of anhydride compound, diamine compound and solvent.
In the resulting polyamic acid resin solution of 100g (solids component weight is 15g), add 0.45g and have isoindole skeleton De perylene mineral black FK4280, stirred three hours, thereby obtain the polyimide resin composition of black.
Use scraping strip coating machine (bar coater) so that the resin layer thickness behind the imidization is the mode of 25 μ m that above-mentioned polyimide resin is coated on the glossy surface of Copper Foil with composition, and 130 ℃ dry 10 minutes down.To apply polyamic acid resin solution and be cooled to room temperature through the exsiccant Copper Foil, heating up then reached 350 ℃ in 5 hours, and with temperature remain on 350 ℃ 30 minutes, naturally cool to room temperature then, thereby obtain double-deck flexible copper-clad veneer sheet.Through removing the Copper Foil on the resulting double-deck flexible copper-clad veneer sheet, obtain the black polyamide film of 25 μ m.
[embodiment 2,3]
The addition that will have isoindole skeleton De perylene mineral black changes the amount shown in the table 1 into, in addition obtains double-deck flexible copper-clad veneer sheet and black polyamide film with embodiment 1 identically.
[comparative example 1]
Use scraping strip coating machine so that the resin layer thickness behind the imidization is the mode of 25 μ m that the polyamic acid resin solution that obtains among the embodiment 1 is coated on the glossy surface of Copper Foil, and 130 ℃ dry 10 minutes down.To apply polyamic acid resin solution and be cooled to room temperature through the exsiccant Copper Foil, heating up then reached 350 ℃ in 5 hours, and temperature was kept 30 minutes at 350 ℃, naturally cooled to room temperature then, thereby obtained double-deck flexible copper-clad veneer sheet.Through removing the Copper Foil on the resulting double-deck flexible copper-clad veneer sheet, obtain the polyimide film of the thick yellow transparent of 25 μ m.
[comparative example 2,3]
The addition that will have isoindole skeleton De perylene mineral black changes the amount shown in the table 2 into, in addition obtains double-deck flexible copper-clad veneer sheet and polyimide film with embodiment 1 identically.
[comparative example 4～6]
Change the kind and the addition of perylene mineral black into the kind shown in the table 2 and amount, in addition obtain double-deck flexible copper-clad veneer sheet and polyimide film identically with embodiment 1.
The foregoing description 1～3 is as shown in table 1, and the evaluation result of comparative example 1～6 is as shown in table 2.
[table 1]
Embodiment 1 Embodiment 2 Embodiment 3
Polyamic acid resin solution (solids component is 15g) 100 100 100
Perylene mineral black class kind FK4280 FK4280 FK4280
Perylene mineral black addition 0.45(3wt％) 0.6(4wt％) 1.2(8wt％)
?CTE(10 -6/K) 19 18 18
Transmittance (%) 3.0 0.2 0.1
?a *Value -3.5 -0.6 -0.1
?b *Value 6.0 3.2 1.2
?L *Value 3.7 2.1 1.1
?Tg(℃) 338 338 338
Breakdown voltage resistant (V/mm) 230 190 170
Specific inductivity 3.49 3.55 3.68
The dielectric tangent 0.003 0.033 0.005
[table 2]
Figure BDA0000053345540000181
Can know that by the result in the table 1 polyimide film (embodiment 1～3) that uses the polyimide resin of this embodiment to obtain with composition has been obtained the well balanced of opacifying property and electrical specification.
Industrial utilization property
The polyimide resin of this embodiment has the industrial utilization property that is applied to metal-coated laminated board, tectum and flexible printing wiring board with composition.

Claims (9)

1. polyimide resin composition, wherein, the perylene mineral black that said polyimide resin contains polyamic acid and has the isoindole skeleton with composition,
With respect to the solids component weight of 100% said polyamic acid in mass, the content of Suo Shu perylene mineral black is in mass 1%～10%.
2. polyimide resin composition according to claim 1, wherein,
Suo Shu perylene mineral black has the structure shown in the following general formula (1),
Figure FDA0000053345530000011
In the formula (1), X representes to have the organic residue of divalence of the isoindole skeleton shown in the following general formula (2),
In the formula (2), R1, R2, R3 and R4 can be identical or different, and expression hydrogen atom or carbonatoms are 1 to 6 alkyl.
3. polyimide resin, wherein, said polyimide resin is to get through claim 1 or 2 described polyimide resins are solidified with composition.
4. metal-coated laminated board, wherein, said metal-coated laminated board is to get through the described polyimide resin layer of claim 3 is pressed on the tinsel.
5. metal-coated laminated board according to claim 4, wherein,
Said metal-coated laminated board is a double-deck flexible metal veneer sheet.
6. tectum, wherein, said tectum comprises the polyimide film that is formed by the described polyimide resin of claim 3.
7. tectum according to claim 6, wherein,
Said tectum also comprises bond layer.
8. tectum according to claim 7, wherein,
Said bond layer contains more than one the resin that is selected from the group of being made up of Resins, epoxy, phenoxy resin, acrylic resin and urethane resin.
9. flexible printing wiring board, wherein, said flexible printing wiring board is to get through each described tectum in the claim 6 to 8 is arranged on the tinsel that is formed with circuit.
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